polymers
Article
Structural, Thermal, and Mechanical Characterization of a
Thermally Conductive Polymer Composite for Heat
Exchanger Applications
Jamieson Brechtl 1, *,† , Yuzhan Li 1,2,† , Kai Li 1 , Logan Kearney 3 , Kashif Nawaz 1, *, Alexis Flores-Betancourt 4 ,
Michael Thompson 5 , Orlando Rios 5 and Ayyoub M. Momen 1






Citation: Brechtl, J.; Li, Y.; Li, K.;
Kearney, L.; Nawaz, K.;
Flores-Betancourt, A.; Thompson, M.;
Rios, O.; Momen, A.M. Structural,
Thermal, and Mechanical
Characterization of a Thermally
Conductive Polymer Composite for
Heat Exchanger Applications.
Polymers 2021, 13, 1970. https://
doi.org/10.3390/polym13121970
Academic Editor: Ana Maria de
Matos Charas
Received: 16 May 2021
Accepted: 12 June 2021
Published: 15 June 2021
Publisher’s Note: MDPI stays neutral
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Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2021, 13, 1970. https://doi.org/10.3390/polym13121970
1 Multifunctional Equipment Research Group, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA;
yuzhanli@ustb.edu.cn (Y.L.); lik1@ornl.gov (K.L.); ayyoubmomen@ultratechsol.com (A.M.M.)
2 School of Materials Science and Engineering, University of Science and Technology Beijing,
Beijing 100083, China
3 Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA; kearneylt@ornl.gov
4 Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA;
floresbetana@ornl.gov
5 Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996, USA;
mthom133@vols.utk.edu (M.T.); orios1@utk.edu (O.R.)
* Correspondence: brechtljm@ornl.gov (J.B.); nawazk@ornl.gov (K.N.)
† These authors contributed equally.
Abstract: Polymer composites are being considered for numerous thermal applications because of
their inherent benefits, such as light weight, corrosion resistance, and reduced cost. In this work, the
microstructural, thermal, and mechanical properties of a 3D printed polymer composite with high
thermal conductivity are examined using multiple characterization techniques. Infrared spectroscopy
and X-ray diffraction reveal that the composite contains a polyphenylene sulfide matrix with graphitic
fillers, which is responsible for the high thermal conductivity. Furthermore, differential scanning
calorimetry determines that the glass transition and melting point of the composite are 87.6 ◦ C and
285.6 ◦ C, respectively. Thermogravimetric analysis reveals that the composite is thermally stable up
to ~400 ◦ C. Creep tests are performed at different isotherms to evaluate the long-term performance
of the composite. The creep result indicates that the composite can maintain mechanical integrity
when used below its glass transition temperature. Nanoindentation tests reveal that modulus and
hardness of the composite is not significantly influenced by heating or creep conditions. These
findings indicate that the composite is potentially suitable for heat exchanger applications.
Keywords: polymer composites; microstructure analysis; thermal analysis; creep modeling; mechan-
ical properties
1. Introduction
Polymer composites are versatile materials and have been used in many applications,
including construction [1–3], oil field [4], energy [5,6], transportation [7], and automation
etc. [8–12]. With interest in cost-effective and durable energy conversion systems growing,
there is an immense focus on the deployment of polymer-based solutions. Applications
such as waste heat recovery, power generation, thermal desalination, and air conditioning
are some obvious examples for which polymer and polymer composite materials are
being considered and, in several cases, successfully deployed to provide sustainable
performance. Waste heat is a form of energy that is a byproduct of almost all mechanical and
thermal processes. This type of energy is produced during industrial processes. Globally,
approximately 247 PJ of energy is discharged as waste heat in exhaust gas and effluents [13].
In the United States, the waste heat resulting from industrial emissions accounted for ~4.3%
of the total energy use by industry as of 2015 [14,15]. More than 80% of this energy was
https://www.mdpi.com/journal/polymers
Polymers 2021, 13, 1970 2 of 14

in the low-temperature regime, which corresponds to temperatures ranging from 25 to

150 ◦ C [15]. Although metallic low-temperature heat recovery systems are available, they
suffer from issues such as high material costs and long payback periods [14].
An alternative to a metallic thermal recovery system is a polymeric heat exchanger.
Compared with other materials (metal alloys and ceramics) deployed in conventional
technologies, polymer-based solutions provide novel characteristics such as higher spe-
cific capacity (kW/kg), opportunities to modulate designs, and effective resistance to
material degradation due to corrosion. A polymer is typically constructed through a
chemical reaction between monomers, resulting in the formation of a long chain composed
of many repeated organic subunits [16]. The wide variety of monomers and reaction
types enables great design flexibility for the control of structure and properties. Further-
more, polymeric materials have desirable properties such as low-temperature processing,
shaping, and joining; resistance to fouling; and corrosion resistance [17]. In terms of corro-
sion resistance, polymeric materials such as polyvinylidene fluoride (PVDF), Teflon, and
polyphenylene sulfide can accommodate highly corrosive environments during exposure
to appreciable mechanical stresses because of their high molecular weight and crystalline
nature [9–12,16,18]. For example, Teflon is resistant to practically all corrosives except
fluorine and molten alkali metals and can withstand temperatures and pressures of up to
204 ◦ C and 862 kPa, respectively [18]. Moreover, heat exchangers composed of polymers
have significantly lower manufacturing costs. For example, Zaheed and Jachuck [18] found
that a heat exchanger composed of PVDF would cost ~40% as much as one composed of a
Ni-Cr-Mo alloy, considering the differences in material cost and density [19].
Despite these positive aspects, there are some major disadvantages associated with the
use of polymers in heat exchanger applications. For example, the lower thermal conductivity
of polymers puts them at a disadvantage compared with steel for use in environments
typical of a heat exchanger [20]. In addition, the long-term performance of polymer heat
exchangers is an important aspect to consider for practical applications. The inherent
viscoelastic properties of polymers make them fundamentally different from other materials.
The mechanical properties of polymers, such as strength and modulus, change with time
because they exhibit characteristics of both an elastic solid and a viscous fluid [21].
In the current study, we focus on characterizing a 3D printed polymer composite with
high thermal conductivity and evaluating its potential use for heat exchanger applications.
The microstructure of the material was characterized using infrared spectroscopy and X-ray
diffraction. We also evaluate the long-term performance of the material using the time–
temperature superposition principle based on short-term creep experiments at different
isotherms. The objective of this study is twofold: to provide the critical attributes of the
material for long-term performance in a typical heat exchanger application and to develop
a framework for the compatibility for a range of potential materials that can be considered
for such an application.

2. Materials and Methods

2.1. Materials and Processing
The filament used for 3D printing was acquired from a commercial vendor. The mate-
rial was commercialized as a high thermal conductivity composite (thermal conductivity
~4 W/m × K). Samples (50 × 50 × 3.18 mm3 ) were additively manufactured using fused
filament fabrication (FFF) on a MakerGear M2 3D printer. Figure 1a,b presents a schematic
representation of a typical FFF process and the printed puck that was used to fabricate the
test samples. The nozzle temperature and diameter, filament diameter, and the layer height
were selected to be 245 ◦ C, 0.75 mm, 1.75 mm, and 0.45 mm, respectively, with 25% overlap.
Furthermore, the heated bed temperature was 75 ◦ C and the print speed was around 30 mm
per second. These parameters are critical because they can impact the characteristics of the
resulting product. They were adopted to ensure that specific geometrical features could be
achieved and could be considered representative parameters for a typical fused filament
fabrication process.
 test samples. The nozzle temperature and diameter, filament diameter, and the layer
height were selected to be 245 °C, 0.75 mm, 1.75 mm, and 0.45 mm, respectively, with 25%
overlap. Furthermore, the heated bed temperature was 75 °C and the print speed was
around 30 mm per second. These parameters are critical because they can impact the char-
Polymers 2021, 13,acteristics
1970 of the resulting product. They were adopted to ensure that specific geometrical 3 of 14
features could be achieved and could be considered representative parameters for a typi-
cal fused filament fabrication process.

Figure
Figure 1. (a) 1. (a) representation
Schematic Schematic representation of a(adapted
of a (FFF) process (FFF) process (adapted
from Ref. from
[22]) and Ref.printed
(b) 3D [22]) and
puck(b) 3Dto
used printed
fabricate
puck
test samples used
(ruler to are
units fabricate test samples (ruler units are in inches).
in inches).

2.2. Structural Analysis

2.2. Structural Analysis
The structure The structure
of the of thewas
composite composite was characterized
characterized using X-ray using X-ray diffraction
diffraction (XRD) and(XRD) and
Fourier-transform infrared spectroscopy (FTIR). XRD revealed crystallinity of the polymer
Fourier-transform infrared spectroscopy (FTIR). XRD revealed crystallinity of the poly-
matrix and graphitic filler, whereas FTIR provided information on the chemical composition
mer matrix andofgraphitic filler, whereas FTIR provided information on the chemical com-
the composite. The XRD experiment was performed using a PANalytical X’Pert Pro
position of thediffractometer.
composite. The TheX-rays
XRD wereexperiment
generatedwas at 45 performed
kV/40 mA, and using a PANalytical
the wavelength of the X-ray
X’Pert Pro diffractometer.
beam was l = 1.541 Å (Cu Ka radiation). The diffraction spectrum waswavelength
The X-rays were generated at 45 kV/40 mA, and the collected over a 2θ
of the X-ray beamrangewas froml 10 to 70◦ Å
= 1.541 at a(Cu
scanKa of 0.15◦ /min.
radiation).
rate TheThe
diffraction spectrum was
FTIR characterization was col-
conducted
lected over a 2θ range
using from 10 toiS50
a NICOLET 70°system
at a scan rateattenuated
in the of 0.15°/min.
total The FTIR characterization
reflectance (ATR) mode. Diamond
was conductedwas usingusedaasNICOLET
the ATR crystal. The FTIR
iS50 system inspectrum was collected
the attenuated at 4 cm−1 resolution
total reflectance (ATR) using
− 1
mode. Diamond was used as the ATR crystal. The FTIR spectrum was collected at 4background.
64 scans from 4000 to 400 cm and corrected against ambient air as the cm−1
Small-angle and wide-angle X-ray scattering (SAXS/WAXS) measurements were carried
resolution using 64 scans from 4000 to 400 cm and corrected against ambient air as the
−1
out on a Xenocs Xeuss 3.0 instrument equipped with D2+ MetalJet X-ray source (Ga Kα,
background. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) measurements
λ = 1.341 Å) to investigate possible preferred orientation and aggregation of the fillers.
were carried out Theon a Xenocs
sample Xeuss perpendicular
was aligned 3.0 instrument equipped
to the direction with D2+
of the MetalJet
X-ray X-ray
beam (transmission
source (Ga Kα,mode)
λ = 1.341 Å) to investigate possible preferred orientation and
and the scattered beam was recorded on a Dectris Eiger 2R 4M hybrid photon aggregation
of the fillers. The sample
counting was aligned
detector perpendicular
with a pixel dimension of to75
the 75 µm2 . The
× direction of collected
the X-ray2-dimensional
beam
(transmission mode) and the scattered
(2D) SAXS/WAXS beamcircularly
images were was recorded averagedon and
a Dectris Eiger
expressed as 2R 4M hy-
intensity versus q,
brid photon counting detector with a pixel dimension of 75 × 75 μm . The collected 2- WAXS
where q = (4π sin θ)/λ after subtraction of background scattering.
2 The SAXS and
dimensional (2D) dataSAXS/WAXS
were collectedimages
at the sample-to-detector
were circularly averaged distance of
and1800 and 55 mm,
expressed respectively.
as inten-
The surface morphology of the material was characterized using a Hitachi 4700-S scanning
sity versus q, where q = (4π sin θ)/λ after subtraction of background scattering. The SAXS
electron microscope (SEM). The polymer was carbon coated to keep it from charging, and a
and WAXS data were collected at the sample-to-detector distance of 1800 and 55 mm,
10 keV accelerating voltage and 20 A of current were used. Three-minute scans were used
respectively. The surfacethe
to generate morphology
compositionofmaps.the material was characterized using a Hitachi
4700-S scanning electron microscope (SEM). The polymer was carbon coated to keep it
from charging,2.3. and Thermal
a 10 keVAnalysis
accelerating voltage and 20 A of current were used. Three-
minute scans were The used to generate
thermal the of
properties composition
the composite maps.
were characterized using thermogravimetric
analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis
2.3. Thermal Analysis and thermomechanical analysis (TMA). The TGA experiment was performed using
(DMA),
a TA Instruments TGA Q50 model. The sample was heated from room temperature to
The thermal properties of the composite were characterized using thermogravimetric
800 ◦ C at 10 ◦ C/min in a nitrogen atmosphere. The DSC experiment was performed using
analysis (TGA), differential
a TA Instruments scanning
DSC 2500calorimetry (DSC), dynamic
model. A heat-cool-heat mechanical
cycle was used withanalysis
a ramp rate of
(DMA), and thermomechanical
20 ◦ C/min under a analysis (TMA). TheThe
nitrogen atmosphere. TGA DMAexperiment
experimentwas
wasperformed us- a TA
performed using
ing a TA Instruments TGA Q50 model. The sample was heated from room temperature
Instruments Q800 model. In the experiment, a rectangular piece (25 × 12.72 × 3.18 to mm3 )
◦ ◦
800 °C at 10 °C/min in a nitrogen
was heated from roomatmosphere.
temperatureThe DSC
to 180 C experiment
at 3 C/min, was
underperformed using
an oscillation frequency
of 1 Hz and at an amplitude of 25 mm in dual-cantilever mode. The TMA experiment was
performed using a model Q400 thermomechanical analyzer (TA Instruments, Inc., New
Polymers 2021, 13, 1970 4 of 14

Castle, Delaware) in expansion mode with a heat-cool-heat cycle at a rate of 3 ◦ C/min. The
second heating scan was recorded to calculate the value of coefficient of thermal expansion
(CTE).
The creep behavior of the polymer composite was investigated using DMA and the
long-term performance was predicted using the time–temperature superposition (TTSP)
principle. Creep tests were carried out using the TA Instruments Q800 DMA in dual-
cantilever mode. Creep tests were performed using a multi-temperature creep and creep
recovery test on a rectangular sample (30 × 3.3 × 1.42 mm3 ). The creep and creep recovery
tests were performed at isotherms from 40 to 110 ◦ C in intervals of 10 ◦ C. A constant stress
of 0.8 MPa was applied for 10 min, followed by a 20 min recovery period at zero stress.
The TTSP principle is commonly used to study the time-dependent mechanical properties
of polymers [23,24]. According to the TTSP principle, a creep experiment conducted at
an elevated temperature is equivalent to one performed for an extended period of time.
Therefore, short-term creep test data collected at different temperature isotherms can be
used to construct a master curve that provides a prediction of the long-term performance
of a polymeric material [25–27]. It is worth mentioning that TTSP exhibits limitations when
multi-phase systems are studied, especially in inhomogeneous systems. However, TTSP
can be applied to multi-component systems that are homogeneous and isotropic.
The creep compliance data were fit according to the Burgers’ four-element model [28].
This type of model consists of a series of combinations of the Maxwell and Kelvin–Voigt
models [29]. The Maxwell model can be represented by an elastic spring and a viscous
damper connected in series, and the Kelvin–Voigt model consists of an elastic spring and a
viscous damper in parallel. The general equation for the model is written as [30]:
t α
h i
J (t) = J0 + J1 1 − e−( τ ) + J2 t (1)

where t is the time elapsed after loading, J0 is the instantaneous creep compliance for small
time scales (~1 s−1 ), J1 is the compliance modulus coefficient associated with the elastic
modulus for the Kelvin-Voigt spring and dashpot, J2 is the compliance coefficient related
to the permanent deformation of the sample, α is the Kohlrausch coefficient [31] (between
0 and 1), and τ is the retardation time. In Equation (1), J0 , J1 , and J2 represent the elastic,
delayed elastic, and viscous behavior of a polymer, respectively, thereby providing a full
picture of the viscoelastic response of the material during the creep test. The retardation
time indicates the intrinsic viscosity of a polymer, as the transient strain in a creep test
occurs as a result of the viscosity of the assembly of molecular chains. Note that permanent
deformation of the sample is associated with slipping of the polymer chains relative to one
another [30].

2.4. Nanoindentation Testing

Nanoindentation tests were performed to determine the hardness and Young’s moduli
of the samples due to their limited size. Samples were cold mounted in epoxy and polished
to a mirror finish (see Figure 2). Indentations were conducted on as-received, heated-
without-creep, and heated-with-creep specimens via a Hysitron TriboIndenter TI-900. The
tests were performed using a standard load transducer with a Berkovich diamond tip that
was calibrated using a standard fused silica sample. A grid of 15 × 15 indents with 50 µm
spacing was made on each sample under displacement control mode with a maximum
depth of ~1000 nm. During the tests, the tip penetrated the sample until it reached the
maximum depth, which was then held for 2 s and subsequently unloaded. The loading
and unloading portions of the experiments were ~5 s each.
Polymers 2021, 13, 1970 5 of 14
Polymers 2021, 13, x FOR PEER REVIEW 5 of 14

Figure2.2.The
Figure Theas-received
as-receivedpolymer
polymernanoindentation
nanoindentationsample
samplethat
thatwas
wascold
coldmounted
mountedininepoxy
epoxyand
and
polished to a mirror finish.
polished to a mirror finish.

3.3.Results
Resultsand
andDiscussion
Discussion
3.1.
3.1.Structure
StructureAnalysis
Analysis
The
TheXRD
XRDspectrum
spectrumofofthe
thepolymer
polymercomposite
compositeisisdisplayed
displayedininFigure
Figure3a;
3a;the
thediffraction
diffraction
peaks ◦ , 20.5◦ , and 36.3◦ suggest that the polymer composite is
peaksatatscattering
scatteringangles
anglesofof18.9
18.9°, 20.5°, and 36.3° suggest that the polymer composite is
composed
composedofofaapolyphenylene
polyphenylenesulfide
sulfide(PPS)
(PPS)matrix
matrix[32–34].
[32–34].Furthermore,
Furthermore,the thediffraction
diffraction
peaks at 26.6 ◦ and 54.7◦ indicate the presence of a graphitic structure that is possibly
peaks at 26.6° and 54.7° indicate the presence of a graphitic structure that is possibly com-
composed of carbon
posed of carbon black,
black, carbon
carbon fiber, fiber, or carbon
or carbon nanotubes.
nanotubes. To confirm
To confirm the chemical
the chemical com-
composition of the polymer matrix, FTIR was utilized and the
position of the polymer matrix, FTIR was utilized and the spectrum, displayed spectrum, displayed in
in Figure
Figure 3b, shows
3b, shows that stretching
that stretching and bending
and bending vibrations
vibrations of the aromatic
of the aromatic structures,
structures, as wellasas
well
carbon–sulfur stretching vibration, occurred [35]. These results suggest that thethat
as carbon–sulfur stretching vibration, occurred [35]. These results suggest the
sample
sample
consisted of a PPS-based polymer matrix. The detailed peak assignments of the XRD the
consisted of a PPS-based polymer matrix. The detailed peak assignments of and
XRD
FTIRand FTIRare
spectra spectra are summarized
summarized in Table 1, in Table 1, confirming
confirming the presence the
of presence of the PPS
the PPS polymer ma-
polymer matrix.
trix. Figure Figure
3c shows the3c
2Dshows
WAXSthe 2D WAXS
pattern of the pattern
polymerofcomposite.
the polymer Thecomposite. The
scattering peaks
scattering peaks correlate well with the diffraction peaks observed in the XRD
correlate well with the diffraction peaks observed in the XRD spectrum. In addition, the spectrum.
In addition, the uniform intensity distribution of the scattering rings confirms that the
uniform intensity distribution of the scattering rings confirms that the material is macro-
material is macroscopically isotropic. Figure 3d shows the 2D SAXS pattern and the
scopically isotropic. Figure 3d shows the 2D SAXS pattern and the integrated 1D scatter-
integrated 1D scattering profile of the polymer composite. The shoulder observed in the
ing profile of the polymer composite. The shoulder observed in the 1D scattering profile
1D scattering profile indicates the presence of an assembled nanostructure with correlation
indicates the presence of an assembled nanostructure with correlation lengths between 67
lengths between 67 and 121 Å, possibly due to the aggregated graphitic fillers.
and 121 Å, possibly due to the aggregated graphitic fillers.
Polymers 2021, 13, x FOR PEER REVIEW 6 of 14
Polymers 2021, 13, 1970 6 of 14

Figure 3. Structural analysis of the polymer composite. (a) XRD spectrum indicating a possible composite structure of PPS
Figure
and 3. Structural
graphite; analysis
(b) FTIR of the
spectrum polymerthe
showing composite.
presence (a) XRD
of an spectrum
aromatic indicating
structure withaapossible composite
carbon–sulfur structure
bond; of PPS
(c) 2D WAXS
and graphite;
pattern (b) FTIR 1D
and integrated spectrum
profile showing theanpresence
confirming isotropicofnature
an aromatic structure with
of the composite; and a(d)
carbon–sulfur bond;and
2D SAXS pattern (c) integrated
2D WAXS
pattern
1D and
profile integrated
showing the 1D profileofconfirming
presence an isotropic
an assembled structurenature of the composite;
with correlation lengthsand (d) 2D67
between SAXS
and pattern
121 Å. and integrated
1D profile showing the presence of an assembled structure with correlation lengths between 67 and 121 Å.

Table 1. XRD and FTIR peak assignment results for the characterized polymer composite.
Table 1. XRD and FTIR peak assignment results for the characterized polymer composite.
XRD
XRD
2 Theta Angle
2 Theta (◦ )
Angle (°) d-Spacing d-Spacing
(Å) (Å) Diffraction Plane Plane
Diffraction
18.918.9 4.69 4.69 (110) of(110)
PPS of PPS
20.520.5 4.33 4.33 (102),(111)
(102), (200), (200),
of(111)
PPS of PPS
26.626.6 3.35 3.35 (002) of(002) of graphite
graphite
36.3 2.47 (004), (302), (311),
(004),(022),
(302),(104),
(311),(213) of (104),
(022), PPS
54.736.3 1.68 2.47 (004) of graphite
(213) of PPS
54.7 1.68
FTIR (004) of graphite
Wavenumber (cm−1 ) FTIR IR Fingerprint
Wavenumber
3050–3150 (cm )
−1
AromaticIR Fingerprint
C-H stretching
3050–3150
1650–1750 Aromatic
Aromatic C-H C-H stretching
bending
1650–1750
1380, 1470, 1573 Aromatic
Aromatic C=C C-H bending
stretching
1060,1091
1380, 1470, 1573 C-S stretching
Aromatic C=C stretching
1009, 804
1060,1091 AromaticC-S C–H bending
stretching
1009, 804 Aromatic C–H bending
3.2. Thermal Analysis
The results of the TGA analysis are presented in Figure 4a. The graph shows the
thermal decomposition behavior of the polymer composite. A maximum decomposition
rate of 0.44% per ◦ C was observed at 531 ◦ C. The sample also shows a high char yield due
 3.2. Thermal Analysis
The results of the TGA analysis are presented in Figure 4a. The graph shows the ther-
mal decomposition behavior of the polymer composite. A maximum decomposition rate
Polymers 2021, 13, 1970 of 0.44% per °C was observed at 531 °C. The sample also shows a high char yield due to
7 of 14
the graphitic fillers and the aromatic structure of PPS [36,37]. For the DSC results, a glass
transition temperature (Tg) of 87.6 °C and melting temperature (Tm) of 285.6 °C were ob-
served,
to theasgraphitic
indicated by the
fillers andstep change and
the aromatic the sharp
structure of PPSpeaks, respectively,
[36,37]. For the DSC ofresults,
the heat a flow
curves
glassin both heating
transition and cooling
temperature (Tg ) of 87.6 ◦
in Figure
C and4b. It should
melting be noted
temperature (Tmthat
) ofthe ◦
step
285.6 C change
were in
theobserved,
DSC curve reflecting
as indicated thestep
by the glass transition
change and theofsharp
the peaks,
material was overshadowed
respectively, of the heat flow by the
curvespeak.
melting in both heating
Figure and cooling
4c shows in Figure
the change 4b. storage
in the It shouldmodulus
be noted andthat tan
the step change
δ of the material
in the DSC curve reflecting the glass transition of the material
as a function of temperature in an oscillatory DMA experiment. A sharp decrease was overshadowed by thein the
melting
storage peak. Figure
modulus 4c showscorresponding
is observed, the change in the tostorage
the glass modulus and tan
transition δ of polymer
of the the material matrix.
as a function of temperature in an oscillatory DMA experiment. A sharp decrease in the
A Tg of 125.3 °C was determined from the peak of the tan δ curve. The values of Tg meas-
storage modulus is observed, corresponding to the glass transition of the polymer matrix. A
ured
Tg by DSC◦ C
of 125.3 and
wasDMA are different,
determined from the peakwhich is not
of the tan δunexpected because
curve. The values of Tgthe underlying
measured
by DSC and DMA are different, which is not unexpected because the underlying propertymoni-
property being monitored was not the same. The Tg measurement in DSC involves
toring a thermodynamic
being monitored was not property
the same. (heatThecapacity), whereasin
Tg measurement the Tg in
DSC DMA ismonitoring
involves obtained from
a viscoelastic property
a thermodynamic (tan δ).
property Figure
(heat 4d shows
capacity), whereas thermal
the Tgexpansion
in DMA isbehavior
obtained of theapoly-
from
merviscoelastic
composite property (tan δ). Figure
characterized using4dTMA. showsThe thermal
CTEexpansion
exhibits behavior of thechange
a noticeable polymerin the
composite
slope when the characterized
temperature using TMA. The
exceeded CTEindicating
~80 °C, exhibits a noticeable change in the
the glass transition. slope
Furthermore,
when the temperature exceeded ~80 ◦ C, indicating the glass transition. Furthermore, the
the composite exhibited excellent dimensional stability with CTE values less than 0.1
composite exhibited excellent dimensional stability with CTE values less than 0.1 µm/◦ C
μm/°C below the glass transition. The thermal analysis results indicate that the polymer
below the glass transition. The thermal analysis results indicate that the polymer matrix
matrix
has ahas a semicrystalline
semicrystalline structure
structure with high with high thermal
thermal and dimensional
and dimensional stability
stability suitable forsuita-
ble heat
for heat exchanger
exchanger applications.
applications.

Figure 4. Thermal analysis of the polymer heat exchanger. (a) TGA curve showing a maximum decomposition rate around
Figure 4. Thermal analysis of the polymer heat exchanger. (a) TGA curve showing a maximum decomposition rate around
531 ◦ C; (b) DSC curve showing a Tg of 87.6 ◦ C and a Tm of 285.6 ◦ C; (c) DMA oscillation showing the evolution of storage
531 °C; (b) DSC curve showing a Tg of 87.6 °C and a Tm of 285.6 °C; (c) DMA oscillation showing the evolution of storage
modulus and tan δ with temperature; and (d) TMA curve showing excellent dimensional stability of the polymer composite.
modulus and tan δ with temperature; and (d) TMA curve showing excellent dimensional stability of the polymer compo-
site.
3.3. Surface Morphology
The results of the SEM characterization of the as-received sample are presented in
Figure 5. A three-phase structure can be observed. This structure consists of a polymer ma-
trix, a graphitic filler (black strips), and an inorganic filler (white dots). Results of the EDS
analysis (see Figure 6) reveal that besides carbon and sulfur, magnesium, silicon, calcium
were present on the surface. The graphitic and inorganic fillers are thought to enhance the
 3.3. Surface Morphology
3.3. Surface Morphology
The results of the SEM characterization of the as-received sample are presented in
FigureThe5. results of the SEM
A three-phase characterization
structure of the This
can be observed. as-received
structuresample are of
consists presented
a polymer in
Polymers 2021, 13, 1970 8 of 14
Figure 5. A three-phase structure can be observed. This structure consists of
matrix, a graphitic filler (black strips), and an inorganic filler (white dots). Results of the a polymer
matrix,
EDS a graphitic
analysis filler (black
(see Figure 6) revealstrips), and an carbon
that besides inorganic
andfiller (white
sulfur, dots). Results
magnesium, of cal-
silicon, the
EDS analysis (see Figure 6) reveal that besides carbon and sulfur, magnesium,
cium were present on the surface. The graphitic and inorganic fillers are thought to en- silicon, cal-
cium were
thermal
hance present conductivity
conductivity
the thermal onandthemechanical
surface.
andThe graphiticofproperties
properties
mechanical and
the inorganic
polymer, fillers are thought
respectively
of the polymer, [38–41].toFor
en-
respectively
hance
instance,the thermal
CaCO hasconductivity
been found and
to mechanical
improve the properties
tensile, of
impact the polymer,
resistance,
[38–41]. For instance, CaCO3 has been found to improve the tensile, impact resistance, and
3 respectively
and flexural
[38–41]. of
strength
flexural Forcertain
instance,
strength CaCOpolymers
ofpolymers
certain has been[40,41].
3[40,41]. found to improve the tensile, impact resistance, and
flexural strength of certain polymers [40,41].

Figure5.5.SEM
Figure SEMimages
imagesshowing
showingaamulti-phase
multi-phasestructure
structureof
ofthe
theas-received
as-receivedsample.
sample.
Figure 5. SEM images showing a multi-phase structure of the as-received sample.

Figure 6. SEM-EDS results that show the presence of elements such as carbon, magnesium, silicon,
Figure6.6.and
calcium,
Figure SEM-EDS results
sulfurresults
SEM-EDS in thatshow
showthe
the as-received
that the presenceof
sample.
presence ofelements
elementssuch
suchas
ascarbon,
carbon,magnesium,
magnesium,silicon,
silicon,
calcium, and sulfur in the as-received sample.
calcium, and sulfur in the as-received sample.
3.4. Creep Test and Modeling
3.4.Creep
3.4. CreepTestTestand
andModeling
Modeling
Figure 7 displays the results for the creep and creep recovery tests performed at iso-
therms Figure
from7740
Figure displays
to 110 °C the
theinresults
results for
forthe
intervals ofthecreep
10 creep and
°C. The andcreep
creep
creep recovery
recovery
behavior tests
of performed
tests
the performed
polymer at iso-
compo-at
therms
isotherms from
from40 to
40 110
to °C
110 ◦ Cintervals
in in of
intervals 10 °C.
of 10 ◦ C.creep
The The behavior
creep of
behaviorthe polymer
of the compo-
polymer
site exhibits a strong temperature dependence, which is caused by the influence of the
site exhibits
composite
glass a strong
exhibits
transition. At alow temperature
strong dependence,
temperature
temperatures °C),which
dependence,
(40–70 is caused
which
the◦ polymer inbya glassy
isiscaused theby influence
the of the
influence
state and the
of the transition.
glass glass transition.
At low At low temperatures
temperatures (40–70 (40–70
°C), the C), the polymer
polymer is in a is in a state
glassy glassy state
and the
movement of the polymer chains is greatly restricted, implying that there was creep re-
and the movement
movement of the polymer
of the polymer ischains
chainsexhibits
greatly is restricted,
greatly restricted,
implying implying
thatcreep
there that
wasthere
creepwas
sistance. Therefore, the material a low and almost constant strain valuere- of
creep resistance.
sistance. Therefore,Therefore,
the the material
material exhibits exhibits
a low a low
and and constant
almost almost constant
creep creepvalue
strain strainof
0.015%. The creep strain value gradually increases from 0.02% at 80 °C to 0.35% at 110 °C,
value
0.015%. of 0.015%.
The creepThestrain
creepvalue
strain value gradually increases from at0.02%°Catto 80 ◦ C to at
0.35% °C, at
indicating
◦ the transition of thegradually
material fromincreases fromstate
a glassy 0.02%to a 80
rubbery 0.35% state. At110 80 °C,
110 C, indicating
indicatingand the
the transition transition of
of thechains the
material material from a glassy state to a rubbery state. At
branches
◦ C, branchesshorter polymer arefrom a glassy
thermally state toand
activated a rubbery
start tostate.
showAt flow80 be-
°C,
80
branches and and shorter
shorter polymer polymer
chains chains
are are thermally
thermally activated
activated and and
start start
to to show
show flowflow
be-
havior; while at 110 °C, ◦ C,longer polymer chains become soft and unentangled, allowing
behavior;
havior; while whileatat110110°C, longer polymer
longer polymer chains
chains become
become softsoft and
and unentangled,
unentangled,allowing allowing
larger deformations. This gradual increase in creep strain from 80 to 110 ◦ C agrees with the
broad glass transition observed in the DSC experiment.
Polymers 2021, 13, x FOR PEER REVIEW 9 of 14

Polymers 2021, 13, 1970

larger deformations. This gradual increase in creep strain from 80 to 110 °C agrees
9 of 14
with
the broad glass transition observed in the DSC experiment.

Figure 7. Creep and creep recovery curves at test temperatures ranging from 40 to 110 ◦ C.
Figure 7. Creep and creep recovery curves at test temperatures ranging from 40 to 110 °C.
The time-dependent creep strain and creep compliance values at different temperature
intervals are shown in Figure
The time-dependent 8a,b.strain
creep The data
andmonotonically
creep compliance increase with respect
values to the test
at different tempera-
temperature. At temperatures
ture intervals are shown in Figure 8a,b. below T , the movement of the polymer
g The data monotonically increase with chains is greatly
respect to
restricted and thus the material exhibits limited creep strain behavior. Assuming that car-
the test temperature. At temperatures below Tg, the movement of the polymer chains is
bon nanotubes are present in the matrix, the resistance of the polymer to creep at relatively
greatly restricted and thus the material exhibits limited creep strain behavior. Assuming
low temperatures (40–70 ◦ C) may be due to certain alignments of the polymer chains and
that carbon
carbon nanotubes
nanotubes that are presentrestrict
effectively in the the
matrix, the resistance
polymer chains fromofstretching,
the polymer to creep at
rotation,
relatively low temperatures (40–70 °C) may be due to certain alignments
refolding, disentanglement as well as sliding under loading [42]. At temperatures above of the polymer
chains
Tg , onand carbon
the other nanotubes
hand, the materialthatiseffectively restrict the
thermally activated, polymer
allowing chainsdeformation.
for larger from stretching,
rotation,
Figure 8c,drefolding,
presentsdisentanglement
the master curvesasthat well as generated
were sliding under from loading [42]. shifted
the manually At tempera-
creep compliance data using 60 ◦ C and 100 ◦ C as the reference temperature, respectively.
tures above Tg, on the other hand, the material is thermally activated, allowing for larger
For example,Figurewhen constructing thethe
master curve ◦ C, all the creep compliance data
for 60 that
deformation. 8c,d presents master curves were generated from the manu-
(Figure 8a) collected at different temperatures (40 C to 110 ◦ C) were first replotted on a
◦
ally shifted creep compliance data using 60 °C and 100 °C as the reference temperature,
log scale. Then, the data collected at temperatures lower than 60 ◦ C were manually shifted
respectively. For example, when constructing the master curve for 60 °C, all the creep
to the left and the data collected at temperatures higher than 60 ◦ C were manually shifted
compliance data (Figure 8a) collected at different temperatures
to the right to form a smooth curve, which represents the long-term performance (40 °C to 110 °C) of were
the first
replotted
materialson a log
when scale. Then,
operating at 60 the
◦ dataa collected
C. For given creep at compliance
temperatures lower
value, 0.04than
GPa 60for
− 1 °C were
manually
example shifted to the
during use at 60 ◦ C,
left andthethe data collected
polymer at temperatures
can stay functional for 27.7 h,higher than
whereas 60 °C were
during
manually ◦ C the service
use at 100shifted to the right to form
time drops a smooth
to 0.44 h. Suchcurve,
a dropwhich represents
in the service the long-term
time indicates that per-
◦
at 100 C,ofthe polymer is highly
formance the materials whensusceptible
operatingtoatcreep,
60 °C. andFor therefore
a givenshould
creepnot be used at value,
compliance
thisGPa
0.04 temperature.
−1 for example during use at 60 °C, the polymer can stay functional for 27.7 h,

whereas during use at 100 °C the service time drops to 0.44 h. Such a drop in the service
time indicates that at 100 °C, the polymer is highly susceptible to creep, and therefore
should not be used at this temperature.
OR PEERPolymers
REVIEW 2021, 13, 1970
10 of 14
10 of 14

Figure 8. Creep behavior of the polymer composite. (a,b) Time-dependent creep strain and creep compliance at different
Figure 8.intervals.
temperature Creep behavior of the
(c,d) Master polymer
curves composite.
generated (a,b)shifted
from manually Time-dependent creep
creep compliance strain
data basedand
on acreep
time–
compliance at different temperature intervals. (c,d) Master curves generated from
temperature superposition principle, which predicts the long-term performance of the material. manually shifted
creep compliance data based on a time–temperature superposition principle, which predicts the
long-term performance ofFigure 9a features the graph for the creep compliance data, J(t), and the correspond-
the material.
ing fitted curves. As can be seen, the fitted curves display an excellent fit to the data.
Figure 9b–f displays the fitting parameters (from Equation (1)) J0 , J1 , J2 , α, and τ as a
Figure 9a features theofgraph
function for the
the testing creep compliance
temperature. data, J(t),coefficients
The creep compliance and the correspond-
J0 and J1 increased
ing fitted curves. As can be seen,
significantly the fitted curves
for temperatures greater display anThe
than 80 ◦ C. excellent
increase fit to compliance
in the the data. Fig-
values J0
ure 9b–f displays the
andfitting
J1 withparameters
temperature are (from
likelyEquation (1)) J0, J1, flexibility
due to the increasing J2, α, and of τpolymer
as a function
chains [43] as
the temperature
of the testing temperature. approaches
The creep the Tg (around
compliance 125.3 ◦ C)J0ofand
coefficients the polymer, as confirmed
J1 increased by the
signifi-
DMA result. Furthermore, this increase in the flexibility of the chains is accompanied by a
cantly for temperatures greater than 80 °C. The increase in the compliance values J0 and J1
decrease in the amount of stored elastic energy as well as a decrease in the storage modulus
with temperature are likely
values [44],due to the
as found increasing
in Figure flexibility
4c. Also, of polymer
these moduli followed achains
similar[43] as thetrend
increasing
temperature approaches
as tan δ.the
TheT g (around
value 125.3 °C)
J2 also exhibited an of the polymer,
increase (nonmonotonic) as confirmed by the tem-
over the prescribed
perature range.
DMA result. Furthermore, This increase
this increase suggests
in the that theof
flexibility polymer chainsis
the chains exhibited a greater by
accompanied amount
of permanent deformation as the temperature increased towards Tg .
a decrease in the amount of stored elastic energy as well as a decrease in the storage mod-
ulus values [44], as found in Figure 4c. Also, these moduli followed a similar increasing
trend as tan δ. The value J2 also exhibited an increase (nonmonotonic) over the prescribed
temperature range. This increase suggests that the polymer chains exhibited a greater
amount of permanent deformation as the temperature increased towards Tg.
 Polymers 2021, 13, x FOR PEER REVIEW 11 of 14
Polymers 2021, 13, 1970 11 of 14

◦ C.
Figure The
9. 9.
Figure fitted
The values
fitted for(a)(a)J(t),
valuesfor (b)J0J,0,(c)
J(t),(b) (c)J1J,1,(d)
(d)JJ22,, (e) α, and
(e) α, and (f)
(f) ττ for
for test
test temperatures
temperatures ranging
ranging from
from 40
40 to
to 110
110 °C.

The Kohlrausch coefficient, on the other hand, initially increased until it attained a
The Kohlrausch coefficient, on the other hand, initially increased until it attained a
maximum value at 80 ◦ C, and then subsequently decreased in value. The Kohlrausch
maximum value at 80 °C, and then subsequently decreased in value. The Kohlrausch co-
coefficient accounts for the distribution of relaxation times and varies between 0 (repre-
efficient accounts for the distribution of relaxation times and varies between 0 (represent-
senting a single relaxation time) and 1 (a wider distribution of relaxation times) [45]. The
ing a single relaxation time) and 1 (a wider distribution of relaxation times) [45]. The ob-
observation that the Kohlrausch coefficient peaked at 80 ◦ C can be explained by the glass
servation that the Kohlrausch coefficient peaked at 80 °C can be explained by the glass
transition of the polymer. As the material passes through the glass transition, the polymer
transition of the polymer. As the material passes through the glass transition, the polymer
chains soften, resulting in a wider distribution of relaxation times. Before or after the glass
chains soften, resulting in a wider distribution of relaxation times. Before or after the glass
transition, however, the polymer chains are completely frozen or relaxed, resulting in a
transition, however, the polymer chains are completely frozen or relaxed, resulting in a
narrower distribution of relaxation times. The retardation time did not show noticeable
narrower distribution of relaxation times. The retardation time did not show noticeable
change within the investigated temperature range.
change within the investigated temperature range.
3.5. Nanoindentation Behavior
3.5. Nanoindentation Behavior
Figure 10 displays the nanoindentation hardness and Young’s modulus results for
Figure 10 displays
the unheated-uncrept, the nanoindentation
heated-uncrept, hardness andsamples
and heated-creeped Young’sthat
modulus results for
were indented in
the unheated-uncrept, heated-uncrept, and heated-creeped samples that
the displacement control mode to a maximum displacement of ~1000 nm. As can be seen, were indented in
the displacement control mode to a maximum displacement of ~1000 nm.
the average hardness and Young’s modulus values range from 0.39 to 0.40 GPa and 6.66 As can be seen,
the
to average
7.28 hardness and(see
GPa, respectively Young’s
Table modulus values range
2). Furthermore, from 0.39
the values to 0.40 one
are within GPastandard
and 6.66
to 7.28 GPa, respectively (see Table 2). Furthermore, the values are within
deviation from one another, indicating that the creep deformation and the heating did one standard
deviation
not from one
significantly another,
change indicating that the
the nanoindentation creep deformation
properties and the
of the polymer. heating
This didalso
finding not
significantly
indicates that change the nanoindentation
there were properties
no significant changes to theofcrystallinity
the polymer. ofThis finding
the PPS alsoand
matrix in-
dicates
filler that there
content. were nothese
Importantly, significant
results changes to the
suggest that thecrystallinity
polymer can ofretain
the PPS matrix and
its mechanical
filler
and content. Importantly,
microstructural these
properties results
when suggest
exposed to that the polymer
the stress can retain
and thermal its mechanical
conditions typical
of a heat exchanger.
Polymers 2021, 13, x FOR PEER REVIEW 12 of 14

Polymers 2021, 13, 1970 12 of 14

and microstructural properties when exposed to the stress and thermal conditions typical
of a heat exchanger.

Figure 10. The

Figure10. The nanoindentation
nanoindentation (a)
(a) hardness
hardness and
and (b)
(b) Young’s
Young’s modulus
modulus for
for the
the unheated
unheated and
and uncrept,
uncrept, heated
heated and
and uncrept,
uncrept,
and
andheated
heatedand
andcreeped
creepedsamples
samplesindented
indentedto
toaamaximum
maximumdisplacement
displacementofof~1000
~1000nm.
nm.

Table2.2.The
Table Thehardness
hardnessand
andYoung’s
Young’smoduli
moduliof
ofthe
theunheated
unheatedand
anduncrept,
uncrept,heated
heatedand
anduncrept,
uncrept,and
and
heated and
heated and creeped
creeped specimens
specimens at
at aa maximum
maximumdisplacement
displacementof
of~1000
~1000 nm.
nm.

Sample
Sample Hardness (GPa)
Hardness (GPa) Young’sModulus
Young’s Modulus(GPa)
(GPa)
Unheated and uncrept 0.40 ± 0.06 7.28 ± 1.34
Unheated and uncrept 0.40 ± 0.06 7.28 ± 1.34
Heated and uncrept 0.39 ± 0.06 6.97 ± 1.42
Heated and uncrept 0.39 ± 0.06 6.97 ± 1.42
Heated and
Heated and crept
crept 0.39 ±± 0.05
0.39 0.05 6.66 ±± 1.28
6.66 1.28

4. Conclusions
4. Conclusions
In this investigation, the structural, thermal, and mechanical properties of a graphite
In this investigation, the structural, thermal, and mechanical properties of a graphite
containing a polymer composite were examined using various experimental techniques.
containing a polymer composite were examined using various experimental techniques.
FTIR and XRD characterization revealed the presence of graphitic fillers in a PPS-based
FTIR and XRD characterization revealed the presence of graphitic fillers in a PPS-based
polymer matrix. Moreover, the DSC results showed that the Tg of the polymer was 87.6
polymer matrix. Moreover, the DSC results showed that the Tg of the polymer was
°C, indicating that the material is potentially suitable for heat exchanger applications.
87.6 ◦ C, indicating that the material is potentially suitable for heat exchanger applications.
Creep tests
Creep tests were
were performed
performedatatdifferent
differentisotherms
isothermstotoenable
enable thetheuse of of
use TTSP to predict
TTSP to predictthe
long-term
the long-term performance
performance of the material,
of the which
material, waswas
which found
foundto be highly
to be temperature-de-
highly temperature-
pendent. Furthermore, the fitting of the time-dependent creep compliance
dependent. Furthermore, the fitting of the time-dependent creep compliance data data correlated
correlated
well with the dynamic mechanical analysis, indicating that the composite
well with the dynamic mechanical analysis, indicating that the composite can retain can retain its
its
mechanical properties when used below its glass transition temperature.
mechanical properties when used below its glass transition temperature. Nanoindentation Nanoindenta-
tion suggested
tests tests suggested that
that the the mechanical
mechanical behaviorbehavior of the composite
of the composite was not was not significantly
significantly affected
affected
by by temperature
temperature or plastic or plastic deformation.
deformation. Based on Based on the
the results results
of this of this
study, study, the
the composite
composite
could be usedcould
forbe used
heat for heat applications
exchanger exchanger applications
where low where
cost and low costdesign
high and high design
flexibility
flexibility
are required. are required.
Notice: This
Notice: This manuscript
manuscript has has been
been authored
authored by by UT-Battelle,
UT-Battelle, LLC LLC under
under Contract
Contract No.No.
DE-AC05-00OR22725 with the U.S. Department of Energy. The United
DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government States Government
retains and
retains and the
the publisher,
publisher,by byaccepting
acceptingthethearticle forfor
article publication,
publication, acknowledges
acknowledges thatthat
the
United
the UnitedStates Government
States Government retains a non-exclusive,
retains a non-exclusive, paid-up,
paid-up, irrevocable,
irrevocable,world-wide
world-wide li-
cense totopublish
license publishor orreproduce
reproduce the the published
published form
form of this manuscript, or allow allow others
others toto
do so,
do so, for
for United
United States
States Government
Government purposes.
purposes. TheThe Department
Department of of Energy
Energy will
will provide
provide
public access
public access to
to these
these results
results of
of federally
federally sponsored
sponsored research
research in in accordance
accordance with
with the
the DOE
DOE
Public Access
Public Access Plan
Plan (http://energy.gov/downloads/doe-public-access-plan,
(http://energy.gov/downloads/doe-public-access-plan, accessed accessed onon13
June
13 June2021).
2021).
Polymers 2021, 13, 1970 13 of 14

Author Contributions: J.B. and Y.L.—investigation, draft writing, conceptualization, methodology;

K.L., M.T., and L.K.—investigation; K.N.—funding, supervision, draft writing; M.T. and A.F.-B.—
investigation; O.R.—supervision; A.M.M.—supervision. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was sponsored by the U. S. Department of Energy’s Building Technologies
Office under Contract No. DE-AC05-00OR22725 with UT-Battelle, LLC.
Acknowledgments: The authors would like to acknowledge Antonio Bouza, Technology Manager—
HVAC&R, Water Heating, and Appliance, U.S. Department of Energy Building Technologies Office.
Conflicts of Interest: The authors declare no conflict of interest.

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